EP3414209A1 - Low-temperature tellurite glass mixtures for vacuum compaction at temperatures of 450 °c - Google Patents

Low-temperature tellurite glass mixtures for vacuum compaction at temperatures of 450 °c

Info

Publication number
EP3414209A1
EP3414209A1 EP17717379.6A EP17717379A EP3414209A1 EP 3414209 A1 EP3414209 A1 EP 3414209A1 EP 17717379 A EP17717379 A EP 17717379A EP 3414209 A1 EP3414209 A1 EP 3414209A1
Authority
EP
European Patent Office
Prior art keywords
glass
weight
range
composite
paste
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP17717379.6A
Other languages
German (de)
French (fr)
Other versions
EP3414209B1 (en
Inventor
Dieter GÖDEKE
Srinivasan Sridharan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Vibrantz GmbH
Original Assignee
Ferro GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ferro GmbH filed Critical Ferro GmbH
Priority to PL17717379T priority Critical patent/PL3414209T3/en
Publication of EP3414209A1 publication Critical patent/EP3414209A1/en
Application granted granted Critical
Publication of EP3414209B1 publication Critical patent/EP3414209B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • C03C27/06—Joining glass to glass by processes other than fusing
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • C03C27/06—Joining glass to glass by processes other than fusing
    • C03C27/10—Joining glass to glass by processes other than fusing with the aid of adhesive specially adapted for that purpose
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/122—Silica-free oxide glass compositions containing oxides of As, Sb, Bi, Mo, W, V, Te as glass formers
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/125—Silica-free oxide glass compositions containing aluminium as glass former
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/14—Silica-free oxide glass compositions containing boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/20—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing titanium compounds; containing zirconium compounds
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/22—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions containing two or more distinct frits having different compositions
    • E—FIXED CONSTRUCTIONS
    • E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
    • E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
    • E06B3/00—Window sashes, door leaves, or like elements for closing wall or like openings; Layout of fixed or moving closures, e.g. windows in wall or like openings; Features of rigidly-mounted outer frames relating to the mounting of wing frames
    • E06B3/66—Units comprising two or more parallel glass or like panes permanently secured together
    • E06B3/6612—Evacuated glazing units
    • E—FIXED CONSTRUCTIONS
    • E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
    • E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
    • E06B3/00—Window sashes, door leaves, or like elements for closing wall or like openings; Layout of fixed or moving closures, e.g. windows in wall or like openings; Features of rigidly-mounted outer frames relating to the mounting of wing frames
    • E06B3/66—Units comprising two or more parallel glass or like panes permanently secured together
    • E06B3/67—Units comprising two or more parallel glass or like panes permanently secured together characterised by additional arrangements or devices for heat or sound insulation or for controlled passage of light
    • E06B3/6715—Units comprising two or more parallel glass or like panes permanently secured together characterised by additional arrangements or devices for heat or sound insulation or for controlled passage of light specially adapted for increased thermal insulation or for controlled passage of light

Definitions

  • the present invention relates to a glass, in particular a glass for joining glass sheets for the production of Vakuumisoliergläsern at
  • the present invention relates to a vacuum insulating glass made with the glass paste of the present invention
  • Glasses used to join glass, ceramic and metal objects are glasses with particularly low softening temperatures. They are also referred to as glass solders or joining glasses.
  • the term "joining” is understood to mean the correct joining or joining of workpieces by appropriate methods (welding, rolling, soldering, etc.).
  • joining glasses are used in the semiconductor sector, in high-temperature fuel cells or in applications in solar cells.
  • the use of joining glasses in the production of vacuum insulating glass has hardly been described.
  • Vacuum insulating glasses are known and already commercially available. At the
  • Vakuumisolierglas the glass space between the two single panes is evacuated. With conventional insulating glass, the glass gap is against
  • the vacuum insulating glass is the
  • the individual disks are usually spaced apart by so-called spacers, which are distributed in a lattice-like manner over the glass surface, so that the external air pressure does not separate the two individual disks
  • Vacuum insulating glass panes are usually produced by placing and fixing spacers on the first individual glass pane and then placing the second individual glass pane on top. This has a in its edge region
  • Contacting pastes for solar cells are used, they are also used as optical amplifiers in Er-doped fiber amplifiers in so-called WDM (wavelength division multiplexing).
  • WDM wavelength division multiplexing
  • tellurium oxide The prices of tellurium oxide vary widely, but tellurium oxide is economically producible at reasonable cost.
  • the glass family has excellent glass formation properties and low melting temperatures not achieved by other conventional glasses.
  • Glass composition consists essentially of Te0 2 and V 2 0 5 and oxides selected from the group consisting of Nb 2 0 5 , Zr0 2 and ZnO, Bi 2 0 3 and CuO and P 2 0 5 and Ta 2 0 5 and furthermore, up to 10% of oxides of zinc, cadmium, barium, Tungsten, molybdenum and titanium.
  • the glasses described here also have no aluminum oxide and the coefficient of expansion is in a range between 14- 18 ⁇ 10 6 / K. The high expansion coefficient is for an application of a
  • WO2013 / 043340 A1 from Guardian describes highly vanadium-containing joining glasses for the production of vacuum insulating glass panes.
  • the main ingredients are
  • Vanadium oxide, barium oxide and zinc oxide Vanadium oxide, barium oxide and zinc oxide.
  • the glasses used here in the vanadium content are very high (between 50-60 wt.%) And they contain no or only very small amounts of tellurium oxide. These glasses are less chemically resistant and more susceptible to crystallization.
  • the V described by F. Wang et al, Materials Letters 67, 196-198 (2012) 2 0. 5 - B 2 0 3 -TE0 2 glasses are different from the present invention in the content of boron oxide.
  • the present invention includes boron-oxide-free glasses.
  • the study shows that the glasses from the system have a partly pronounced
  • the described paste comprises silver as the main constituent, a glass frit and an organic support, wherein the glass frit contains tellurium oxide as a network forming component and further tungsten and molybdenum oxide. Chemically, the glasses described here differ by the content of tungsten oxide (WO 3 ) and the absence of vanadium pentoxide.
  • CN101164942 A discloses a lead-free tellurate glass of tellurium oxide and vanadium oxide in which small amounts of zinc oxide or aluminum oxide may be present.
  • US2014 / 008587A1 describes a conductive paste comprising a glass frit comprising tellurium as a network-forming component in an amount of 35 to 70 mole% based on the oxide.
  • silver is present in an amount of 3 to 40 mol%, based on the oxide, and also tungsten and molybdenum may be present.
  • vanadium oxide is not mentioned.
  • JP 2004356394A describes a sealing material which contains a glass component which, in addition to vanadium pentoxide and tellurium dioxide, may contain up to 10% zinc oxide and small amounts of aluminum oxide.
  • Bismuth-containing glasses fail in use because these glasses are very sensitive to crystallization and they are from the start of softening above 400 ° C. In addition, their flow behavior is greatly affected by the addition of fillers, which reduces the wettability of the glasses with their composite material.
  • PCT / EP2015 / 072207 describes low temperature tellurite bonding glasses for joining vacuum insulating glass and for other applications such as MEMS joining at 420 ° C. Many such joining processes take place not only at atmospheric pressure but also in reduced pressure applications such as light vacuum (about 100-600 mbar), medium vacuum (0.01-100 mbar) and high vacuum ( ⁇ 0.01 mbar). In this case, depending on the glass composition and the thickness and the type of Bonding materials before sintering larger pores are generated due to a reduction of the components in glass or simply by enlarging the remaining pores in the joining structures. Thus, new approaches are needed to achieve satisfactory results when added under vacuum above the glass transition temperature Tg of the joining glass.
  • the present invention aims to reduce pore formation
  • Product glass is performed, which was melted at the joining temperature (at atmospheric pressure or slight vacuum conditions) and then subjected to a vacuum above the Tg of the joining glass.
  • the invention provides several options:
  • Joined mixture can be added or
  • joining glass which comprises the following components% by weight:
  • Te0 2 -V 2 0 5 glass in the range of 60-100 wt .-%
  • High temperature glasses selected from the group consisting of lead glass, bismuth glass, zinc glass, barium glass, ceria glass, alkali silicate glass in the range of 0-20% by weight, and
  • reactive oxides selected from the group consisting of Al 2 0 3, Y2O3, La 2 0 3, ZnO, Bi 2 0 3, Si0 2, Zr0 2, zircon, Nb 2 0 5, V 2 0 5, Te0 2 CeO 2 , SnO, SnO 2 , FeO, MnO,
  • a preferred embodiment is when Te0 2 -V 2 0s glass
  • High temperature glasses selected from the group consisting of lead glass, bismuth glass, zinc glass, barium glass, ceria glass, alkali silicate glass in the range of
  • Vacuum insulating glass panes is as follows:
  • the Te0 2 -V 2 0 5 glass is preferably made
  • the high-temperature glass is preferably made of bismuth glass, with
  • the reactive oxides are preferably selected from the group consisting of Al 2 0 3, Y 2 O 3, La 2 0 3, ZnO, Bi 2 0 3, Si0 2, Zr0 2, zircon, Nb 2 0 5 or combinations thereof ,
  • the reactive oxides are particularly preferably selected from the group consisting of Al 2 O 3 , Y 2 O 3 , Bi 2 O 3 , ZnO or combinations thereof.
  • Another aspect of the invention is a composite glass, in addition to the
  • glass according to the invention further comprises a filler.
  • This filler is in the range of 1 to 25% by weight and is selected from cordierite or eucryptite. Preferred is a filler range of 20-25 wt .-%.
  • the invention further provides a glass paste which is produced from the glass according to the invention or from the composite glass according to the invention by means of a screen-printing medium. It is preferred that the glass paste comprises a binder. Here preferably a polypropylene carbonate is used.
  • Another object of the invention is a method for producing a
  • Vacuum insulating glazing In the method shown here, the glass solder according to the invention is used in the form of a paste, which should, however, only be illustrated by way of example. Alternatively, the glass solder itself or the composite material can also be used to produce a vacuum insulating glass. The process is characterized by the following steps:
  • Another object of the invention is the vacuum insulating glass, which was prepared by the method described above.
  • the glass solder according to the invention, the composite glass according to the invention and the glass paste according to the invention are used as joining material for glass panes for the production of vacuum insulating glasses.
  • tellurium oxide powder 75-80% d50 3-10 ⁇
  • the raw materials are thoroughly mixed in a planetary mixer, paddle mixer, etc. and melted in a ceramic crucible, refractory under air at 650-750 ° C in an electric furnace.
  • the low melting temperatures are necessary to prevent evaporation of the TeC> 2.
  • Oxidizing melt routing is necessary, but no 02 bubbling.
  • Quenching may be in water or alternatively on water-cooled rolls.
  • the glass has a reddish, brown black color. Quenching the glass is not trivial due to the low viscosity of the glass on a roll.
  • a casting is recommended at temperatures of approx. 650 ° C.
  • the quenched frit in ball mills, jet mills, etc. is ground to particle sizes d90 ⁇ 60 ⁇ .
  • the CTE can be adjusted either during grinding by adding a ceramic filler or in a final mixing step.
  • the glass is processed with a screen printing medium 801022 or 801026 via a three-roll mill to form a paste.
  • the glass may be processed with a polypropylene carbonate binder (e.g., QPac 40 binder company: Empower materials, USA).
  • a polypropylene carbonate binder e.g., QPac 40 binder company: Empower materials, USA.
  • This binder has the advantage that it decomposes at temperatures between 250-300 ° C and thus ensures that no carbon residues in the joining glass
  • the glass solder-coated float glass in an oven with electrically heated infrared elements to a temperature of 300 ° C and held there for 30-60 minutes, then heated to the bonding temperature of 325-390 ° C, held for 1-5 minutes and cooled again to room temperature.
  • the second float glass pane can be placed on the pre-coated float glass pane and mechanically fixed by means of clamping. Spacers between the discs ensure a uniform height of solder.
  • the composite is brought directly to the bonding temperature of 325- 390 ° C and held there for 10-15 minutes. Finally, the composite is cooled again to room temperature. This process ensures that the composite is largely free of pores, since the binder was previously burned out at 300 ° C. Individual process steps are carried out at reduced atmospheric pressure such as light vacuum (about 100-600 mbar), medium vacuum (about 0.1-100 mbar) and high vacuum ( ⁇ 0.01 mbar) to control pore formation.
  • High-temperature glasses selected from the group consisting of lead glass, bismuth glass, zinc glass, barium glass, calcium glass, alkali silicate glass in the range of 0.5-20% by weight were added to the joining glass mixtures from PCT / EP2015 / 072207.
  • lead glass bismuth glass
  • zinc glass barium glass
  • calcium glass alkali silicate glass in the range of 0.5-20% by weight
  • reactive oxides selected from the group consisting of Al 2 O 3 , Y 2 O 3 , La 2 O 3 , ZnO, Bi 2 O 3 , SiO 2 , ZrO 2 , zirconium, Nb 2 O 5 , V 2 O 5 , TeO 2 , CeO 2 , SnO, SnO 2 , FeO,
  • the particle size of the reactive oxides is 0.1 to 40 ⁇ , preferably 0.1 to 20 ⁇ .
  • Preferred reactive oxides Y 2 O 3 , ZnO, Bi 2 O 3 , Al 2 O 3
  • Inert gas N 2 or argon
  • Example 1 Addition of various amounts of a bismuth-containing glass to a tellurium vanadium glass To TDF9533a were added 5% by weight and 10% by weight of EG9824, respectively.
  • TDF9533a composition TeO 2 56.00 wt.%, V 2 O 5 32.00 wt.% And Al 2 O 3 12.00 wt.%
  • EG9824A7 Bi 2 O 3 -ZnO-B 2 O 3 glass.
  • Table 1 clearly shows the increase in the softening point and the respective temperatures with increasing concentration of EG9824.
  • a particle size of cordierite of d50 has proven to be suitable for approximately 20 ⁇ m.
  • FIG. 1 shows the dependence of the sphere temperature on the volume concentration of the additive.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Glass Compositions (AREA)
  • Photovoltaic Devices (AREA)

Abstract

The invention relates to a glass, in particular a glass for joining glass panes in order to produce vacuum insulated glasses at processing temperatures of ≤ 450 °C, to the corresponding composite glass, and to the corresponding glass paste. The invention further relates to a vacuum insulated glass produced by means of the glass paste according to the invention, to the production method thereof, and to the use of the glass according to the invention or of the composite glass and of the glass paste. The glass according to the invention is characterized in that said glass comprises the following components in wt%: TeO2-V2O5 glass in the range of 60-100 wt%, high temperature glasses, selected from the group consisting of lead glass, bismuth glass, zinc glass, barium glass, calcium glass, alkali silicate glass, in the range of 0-20 wt%, and reactive oxides, selected from the group consisting of Al2O3, Y2O3, La2O3, ZnO, Bi2O3, SiO2, ZrO2, zircon, Nb2O5, V2O5, TeO2, CeO2, SnO, SnO2, FeO, MnO, Cr2O3, CoO, oxide pigments, or a combination thereof, in the range of 0-20 wt%.

Description

Niedertemperatur-Telluritglasmischungen für Vakuumverdichtung bei  Low-temperature tellurite glass mixtures for vacuum compression at
Temperaturen <450 °C  Temperatures <450 ° C
Beschreibung description
Die vorliegende Erfindung bezieht sich auf ein Glas, insbesondere auf ein Glas zum Fügen von Glasscheiben zur Herstellung von Vakuumisoliergläsern bei The present invention relates to a glass, in particular a glass for joining glass sheets for the production of Vakuumisoliergläsern at
Verarbeitungstemperaturen < 450 °C, auf das entsprechende Kompositglas und auf die entsprechende Glaspaste. Ferner bezieht sich die vorliegende Erfindung auf ein Vakuumisolierglas, hergestellt mit der erfindungsgemäßen Glaspaste, auf das Processing temperatures <450 ° C, on the appropriate composite glass and on the appropriate glass paste. Further, the present invention relates to a vacuum insulating glass made with the glass paste of the present invention
Herstellungsverfahren davon und auf die Verwendung des erfindungsgemäßen Glases bzw. des Kompositglases und der Glaspaste.  Production method thereof and to the use of the glass or the composite glass according to the invention and the glass paste.
Stand der Technik State of the art
Gläser, die zum Verbinden von Gegenständen aus Glas-, Keramik- und Metallteilen verwendet werden, sind Gläser mit besonders niedrigen Erweichungstemperaturen. Sie werden auch als Glaslote oder Fügegläser bezeichnet. Unter dem Ausdruck„Fügen" wird das korrekte Aneinanderbringen oder Verbinden von Werkstücken durch entsprechende Verfahren (Schweißen, Walzen, Löten usw.) verstanden. Glasses used to join glass, ceramic and metal objects are glasses with particularly low softening temperatures. They are also referred to as glass solders or joining glasses. The term "joining" is understood to mean the correct joining or joining of workpieces by appropriate methods (welding, rolling, soldering, etc.).
Glaslote oder Fügegläser sind im Stand der Technik umfangreich beschrieben.  Glass solders or joining glasses are extensively described in the prior art.
Insbesondere kommen Fügegläser im Halbleiterbereich, bei Hochtemperatur- Brennstoffzellen oder auch bei Anwendungen in Solarzellen zum Einsatz. Der Einsatz von Fügegläsern bei der Herstellung von Vakuumisolierglasscheiben wurde allerdings bisher kaum beschrieben. Vakuumisoliergläser sind bekannt und auch bereits kommerziell erhältlich. Beim In particular, joining glasses are used in the semiconductor sector, in high-temperature fuel cells or in applications in solar cells. However, the use of joining glasses in the production of vacuum insulating glass has hardly been described. Vacuum insulating glasses are known and already commercially available. At the
Vakuumisolierglas ist der Glaszwischenraum zwischen den beiden Einzelscheiben evakuiert. Bei herkömmlichem Isolierglas ist der Glaszwischenraum dagegen Vakuumisolierglas the glass space between the two single panes is evacuated. With conventional insulating glass, the glass gap is against
üblicherweise mit einem Edelgas gefüllt. Auch ist beim Vakuumisolierglas der usually filled with a noble gas. Also, the vacuum insulating glass is the
Glaszwischenraum aufgrund der fehlenden Konvektion zwischen den beiden Glass space due to the lack of convection between the two
Einzelscheiben erheblich geringer. Die Einzelscheiben sind üblicherweise durch sogenannte Abstandshalter, die gitterartig über die Glasfläche verteilt angeordnet sind, beabstandet, damit der äußere Luftdruck die beiden Einzelscheiben nicht Single slices considerably lower. The individual disks are usually spaced apart by so-called spacers, which are distributed in a lattice-like manner over the glass surface, so that the external air pressure does not separate the two individual disks
zusammendrücken kann und sind an den Rändern durch einen Randverbund can squeeze and are at the edges by an edge bond
vollumfänglich miteinander verbunden. fully interconnected.
Vakuumisolierglasscheiben werden üblicherweise hergestellt, indem auf die erste Einzelglasscheibe Abstandshalter aufgesetzt und fixiert werden und anschließend die zweite Einzelglasscheibe aufgelegt wird. Diese weist in ihrem Randbereich eine Vacuum insulating glass panes are usually produced by placing and fixing spacers on the first individual glass pane and then placing the second individual glass pane on top. This has a in its edge region
Bohrung mit Absaugstutzen für die nachfolgende Evakuierung auf. Die Verbindung der beiden Glasscheiben entlang ihrer Ränder findet beispielsweise mittels Glaslot statt. Während tellurhaltige Gläser als Fasermaterialien und in leitfähigen Bore with suction for subsequent evacuation on. The connection of the two glass panes along their edges takes place for example by means of glass solder. While tellurhaltige glasses as fiber materials and in conductive
Kontaktierungspasten für Solarzellen Einsatz finden, sind sie auch als optische Verstärker in Er-dotierten Faserverstärkern in sogenannten WDM (wavelength division multiplexing) im Einsatz. Im Bereich der Lotgläser und Verbindungsgläser sind sie noch weitgehend unbekannt. Insbesondere für den Einsatz zur Herstellung von Vakuumisoliergläsern sind sie nicht beschrieben. Contacting pastes for solar cells are used, they are also used as optical amplifiers in Er-doped fiber amplifiers in so-called WDM (wavelength division multiplexing). In the field of solder glasses and connecting glasses, they are still largely unknown. In particular, they are not described for use in the manufacture of vacuum insulating glasses.
Die Preise für Telluroxid schwanken stark, allerdings ist Telluroxid wirtschaftlich mit vertretbaren Kosten herstellbar. Die Glasfamilie besitzt herausragende Eigenschaften hinsichtlich Glasbildung und niedrigen Schmelztemperaturen, die von anderen herkömmlichen Gläsern nicht erreicht werden.  The prices of tellurium oxide vary widely, but tellurium oxide is economically producible at reasonable cost. The glass family has excellent glass formation properties and low melting temperatures not achieved by other conventional glasses.
US5,188,990 beschreibt Tellur- Vanadat-Gläser für Halbleiter-Anwendungen (sog. Cer- Dip-Packages ). Fügepartner stellen Keramiken: Aluminiumoxid dar. Die No. 5,188,990 describes tellurium vanadate glasses for semiconductor applications (so-called cerium dip packages). Mating partners represent ceramics: alumina. The
Glaszusammensetzung besteht im Wesentlichen aus Te02 und V205 und Oxiden, ausgewählt aus der Gruppe, die aus Nb205, Zr02 und ZnO, Bi203 und CuO und P205 und Ta205 besteht und ferner bis zu 10% aus Oxiden von Zink, Cadmium, Barium, Wolfram, Molybdän und Titan. Die hier beschriebenen Gläser weisen zudem kein Aluminiumoxid auf und der Ausdehnungskoeffizient liegt in einem Bereich zwischen 14- 18 ■ 106/ K. Der hohe Ausdehnungskoeffizient ist für eine Anwendung einer Glass composition consists essentially of Te0 2 and V 2 0 5 and oxides selected from the group consisting of Nb 2 0 5 , Zr0 2 and ZnO, Bi 2 0 3 and CuO and P 2 0 5 and Ta 2 0 5 and furthermore, up to 10% of oxides of zinc, cadmium, barium, Tungsten, molybdenum and titanium. The glasses described here also have no aluminum oxide and the coefficient of expansion is in a range between 14- 18 ■ 10 6 / K. The high expansion coefficient is for an application of a
Glas/Glas-Fügung von Nachteil, da mit einem höheren Gehalt von Füllstoffen gearbeitet werden muss. Die hier verwendeten Füllstoffe, u.a. Niobpentoxid, sind zudem von Nachteil. Eine Glas / Glas-Fügung wurde nicht untersucht. Glass / glass joining disadvantage, since it must be worked with a higher content of fillers. The fillers used here, i.a. Niobium pentoxide, are also disadvantageous. A glass / glass addition has not been investigated.
WO2013/043340 A1 der Firma Guardian beschreibt hoch Vanadium-haltige Fügegläser für die Herstellung von Vakuumisolierglasscheiben. Die Hauptbestandteile sind WO2013 / 043340 A1 from Guardian describes highly vanadium-containing joining glasses for the production of vacuum insulating glass panes. The main ingredients are
Vanadiumoxid, Bariumoxid und Zinkoxid. Die hier verwendeten Gläser sind jedoch im Vanadium-Gehalt sehr hoch (zwischen 50-60 Gew.%) und sie enthalten keine oder nur sehr geringe Mengen an Telluroxid. Diese Gläser sind chemisch weniger resistent und anfälliger in Bezug auf Kristallisation. Die von F. Wang et al., Materials Letters 67, 196-198 (2012) beschriebenen V205- B203-Te02-Gläser unterscheiden sich von der vorliegenden Erfindung im Gehalt von Boroxid. Die vorliegende Erfindung umfasst boroxidfreie Gläser. Zudem belegt die Studie, dass die Gläser aus dem System eine zum Teil ausgeprägte Vanadium oxide, barium oxide and zinc oxide. However, the glasses used here in the vanadium content are very high (between 50-60 wt.%) And they contain no or only very small amounts of tellurium oxide. These glasses are less chemically resistant and more susceptible to crystallization. The V described by F. Wang et al, Materials Letters 67, 196-198 (2012) 2 0. 5 - B 2 0 3 -TE0 2 glasses are different from the present invention in the content of boron oxide. The present invention includes boron-oxide-free glasses. In addition, the study shows that the glasses from the system have a partly pronounced
Kristallisationsneigung (unterhalb 400°C) aufweisen. Crystallization tendency (below 400 ° C) have.
In US8,551 ,368B2 werden tellurhaltige Gläser für die Anwendung in In US8,551, 368B2 tellurium-containing glasses for use in
Solarzellenkontaktierungspasten beschrieben. Die beschriebene Paste umfasst Silber als Hauptbestandteil, eine Glasfritte und einen organischen Träger, wobei die Glasfritte Telluroxid als netzwerkbildenden Bestandteil und ferner Wolfram- und Molybdänoxid enthält. Chemisch unterscheiden sich die hier beschriebenen Gläser durch den Gehalt an Wolframoxid (WO3) und das Fehlen von Vanadiumpentoxid. Solar cell contacting pastes described. The described paste comprises silver as the main constituent, a glass frit and an organic support, wherein the glass frit contains tellurium oxide as a network forming component and further tungsten and molybdenum oxide. Chemically, the glasses described here differ by the content of tungsten oxide (WO 3 ) and the absence of vanadium pentoxide.
Die US2010/0180934A1 beschreibt eine Glaszusammensetzung mit niedrigem US2010 / 0180934A1 describes a low glass composition
Erweichungspunkt für elektronische Bauteile, die im Wesentlichen frei von Blei, Bismut und Antimon ist. Der Vanadiumoxidgehalt beträgt 40-65 Gewichtsprozent und der Tellurgehalt ist mit 20-30 Gewichtsprozent relativ gering. Die CN101164942 A offenbart ein bleifreies Telluratglas aus Telluoroxid und Vanadiumoxid, bei dem geringe Mengen an Zinkoxid oder Aluminiumoxid zugegen sein können. US2014/008587A1 beschreibt eine leitfähige Paste, die eine Glasfritte umfasst, die Tellur als netzwerkbildenden Bestandteil in einer Menge von 35 bis 70 mol%, bezogen auf das Oxid, umfasst. Daneben ist noch Silber in einer Menge von 3 bis 40 mol%, bezogen auf das Oxid, vorhanden und auch Wolfram und Molybdän können vorhanden sein. Der Zusatz von Vanadiumoxid wird nicht erwähnt. Softening point for electronic components, which is essentially free of lead, bismuth and antimony. The vanadium oxide content is 40-65 weight percent and the tellurium content is relatively low at 20-30 weight percent. CN101164942 A discloses a lead-free tellurate glass of tellurium oxide and vanadium oxide in which small amounts of zinc oxide or aluminum oxide may be present. US2014 / 008587A1 describes a conductive paste comprising a glass frit comprising tellurium as a network-forming component in an amount of 35 to 70 mole% based on the oxide. In addition, silver is present in an amount of 3 to 40 mol%, based on the oxide, and also tungsten and molybdenum may be present. The addition of vanadium oxide is not mentioned.
Die JP 2004356394A beschreibt ein Dichtungsmaterial, welches eine Glaskomponente enthält, die neben Vanadiumpentoxid und Tellurdioxid Zinkoxid bis zu 10 % und geringe Mengen an Aluminiumoxid enthalten kann. Bei den Herstellungsverfahren für Vakuumisolierglasscheiben vom Stand der Technik gibt es gewisse Grenzen. Ein Nachteil ist insbesondere die zum Teil sehr hohe JP 2004356394A describes a sealing material which contains a glass component which, in addition to vanadium pentoxide and tellurium dioxide, may contain up to 10% zinc oxide and small amounts of aluminum oxide. There are certain limits in the manufacturing processes for vacuum insulating glass panes of the prior art. A disadvantage is especially the sometimes very high
Fügetemperatur. Joining temperature.
Aktuell werden Fügetemperaturen kleiner als 400°C nur mit hoch bleihaltigen Currently, joining temperatures less than 400 ° C only with high lead-containing
Fügegläsern erzielt, deren chemische Beständigkeit als nicht ausreichend angesehen werden kann und die aus Umweltgesichtspunkten eine globale Markteinführung behindern. Bismut-haltige Gläser scheitern in der Anwendung, da diese Gläser sehr kristallisationsempfindlich sind und sie vom Erweichungsbeginn oberhalb von 400 °C liegen. Außerdem wird Ihr Fließverhalten stark durch die Zugabe mit Füllstoffen beeinträchtigt, was die Benetzbarkeit der Gläser mit ihrem Verbundwerkstoff herabsetzt. Gives joining glasses whose chemical resistance can not be considered sufficient and which hinder a global market introduction from an environmental point of view. Bismuth-containing glasses fail in use because these glasses are very sensitive to crystallization and they are from the start of softening above 400 ° C. In addition, their flow behavior is greatly affected by the addition of fillers, which reduces the wettability of the glasses with their composite material.
PCT/EP2015/072207 beschreibt Niedertemperatur-Telluritfügegläser zum Fügen von Vakuumisolierglas und für andere Anwendungen wie MEMS-Fügen bei ^ 420°C. Viele solcher Fügeprozesse finden nicht nur bei Atmosphärendruck statt, sondern auch bei Anwendungen unter reduziertem Druck wie leichtes Vakuum (ca. 100-600mbar), mittleres Vakuum (0,01 -100 mbar) und Hochvakuum (<0,01 mbar). Dabei können in Abhängigkeit von der Glaszusammensetzung und der Dicke und des Typs an Fügematerialien vor dem Sintern größere Poren erzeugt werden, aufgrund einer Reduktion der Komponenten in Glas oder einfach durch Vergrößerung der restlichen Poren in den Fügestrukturen. Somit sind neue Herangehensweisen notwendig, um bei der Fügung unter Vakuum oberhalb der Glasübergangstemperatur Tg des Fügeglases zufriedenstellende Ergebnisse zu erzielen. PCT / EP2015 / 072207 describes low temperature tellurite bonding glasses for joining vacuum insulating glass and for other applications such as MEMS joining at 420 ° C. Many such joining processes take place not only at atmospheric pressure but also in reduced pressure applications such as light vacuum (about 100-600 mbar), medium vacuum (0.01-100 mbar) and high vacuum (<0.01 mbar). In this case, depending on the glass composition and the thickness and the type of Bonding materials before sintering larger pores are generated due to a reduction of the components in glass or simply by enlarging the remaining pores in the joining structures. Thus, new approaches are needed to achieve satisfactory results when added under vacuum above the glass transition temperature Tg of the joining glass.
Aus diesem Grund wurde die vorliegende Erfindung fertiggestellt. For this reason, the present invention has been completed.
Aufgabe task
Die vorliegende Erfindung hat zum Ziel, die Porenbildung unter The present invention aims to reduce pore formation
Vakuumbrennbedingungen zu steuern, indem eine Viskositätskontrolle des To control vacuum firing conditions by a viscosity control of the
Produktglases durchgeführt wird, welches bei Fügetemperatur (bei Atmosphärendruck oder leichten Vakuumbedingungen) geschmolzen wurde und anschließend einem Vakuum oberhalb der Tg des Fügeglases ausgesetzt wird. Product glass is performed, which was melted at the joining temperature (at atmospheric pressure or slight vacuum conditions) and then subjected to a vacuum above the Tg of the joining glass.
Detaillierte Beschreibung der Erfindung Detailed description of the invention
Zur Steuerung der Viskosität stellt die Erfindung mehrere Möglichkeiten bereit: To control the viscosity, the invention provides several options:
a) Bereitstellen eines Te02-V205-Glases und a) providing a Te0 2 -V 2 0 5 glass and
b) Zugabe von Hochtemperaturgläsern oder  b) addition of high temperature glasses or
c) Zugabe von reaktiven Füllern, hauptsächlich auf Oxidbasis, die zu der  c) addition of reactive fillers, mainly based on oxide, to the
Fügemischung zugegeben werden oder  Joined mixture can be added or
d) Kombinationen von a) mit b) und c).  d) combinations of a) with b) and c).
Die oben genannte Aufgabe konnte durch die Bereitstellung eines Glases, The above object has been achieved by providing a glass,
insbesondere Fügeglases, gelöst werden, das die nachfolgenden Komponenten Gew.-% umfasst: in particular joining glass, which comprises the following components% by weight:
Te02-V205-Glas im Bereich von 60-100 Gew.-%, Hochtemperaturgläser, ausgewählt aus der Gruppe, die aus Bleiglas, Bismutglas, Zinkglas, Bariumglas, Caiciumglas, Alkalisilikatglas im Bereich von 0-20 Gew.-% besteht und Te0 2 -V 2 0 5 glass in the range of 60-100 wt .-%, High temperature glasses selected from the group consisting of lead glass, bismuth glass, zinc glass, barium glass, ceria glass, alkali silicate glass in the range of 0-20% by weight, and
reaktive Oxide, ausgewählt aus der Gruppe, die aus Al203, Y2O3, La203, ZnO, Bi203, Si02, Zr02, Zircon, Nb205, V205, Te02, Ce02, SnO, Sn02, FeO, MnO,reactive oxides selected from the group consisting of Al 2 0 3, Y2O3, La 2 0 3, ZnO, Bi 2 0 3, Si0 2, Zr0 2, zircon, Nb 2 0 5, V 2 0 5, Te0 2 CeO 2 , SnO, SnO 2 , FeO, MnO,
Cr203, CoO, Oxidpigmenten, oder einer Kombination davon, im Bereich von 0-20 Gew.-% besteht. Cr 2 O 3, CoO, oxide pigments, or a combination thereof, in the range of 0-20% by weight.
Eine bevorzugte Ausführungsform ist es, wenn Te02-V20s-Glas, A preferred embodiment is when Te0 2 -V 2 0s glass,
Hochtemperaturgläser und reaktive Oxide zum Einsatz kommen: High temperature glasses and reactive oxides are used:
Te02-V205-Glas im Bereich von 60-100 Gew.-%, Te0 2 -V 2 0 5 glass in the range of 60-100 wt .-%,
Hochtemperaturgläser, ausgewählt aus der Gruppe, die aus Bleiglas, Bismutglas, Zinkglas, Bariumglas, Caiciumglas, Alkalisilikatglas im Bereich von  High temperature glasses, selected from the group consisting of lead glass, bismuth glass, zinc glass, barium glass, ceria glass, alkali silicate glass in the range of
0,5-20 Gew.-% besteht und  Consists of 0.5-20 wt .-% and
- reaktive Oxide, ausgewählt aus der Gruppe, die aus Al203, Y203, La203, ZnO, Bi203, Si02, Zr02, Zircon, Nb205, V205, Te02, Ce02, SnO, Sn02, FeO, MnO, Cr203, CoO, Oxidpigmenten, oder einer Kombination davon, im Bereich von 0,5-20 Gew.-% besteht. Das Anforderungsprofil eines Fügeglases/Komposites als Lot für - reactive oxides selected from the group consisting of Al 2 0 3, Y 2 0 3, La 2 0 3, ZnO, Bi 2 0 3, Si0 2, Zr0 2, zircon, Nb 2 0 5, V 2 0 5 , TeO 2 , CeO 2 , SnO, SnO 2 , FeO, MnO, Cr 2 O 3 , CoO, oxide pigments, or a combination thereof, in the range of 0.5-20% by weight. The requirement profile of a joining glass / composite as a solder for
Vakuumisolierglasscheiben ist wie nachfolgend: Vacuum insulating glass panes is as follows:
Fügetemperatur < 400°C  Bonding temperature <400 ° C
Thermischer Ausdehnungskoeffizient des Kompositglases (Fügeglas +  Thermal expansion coefficient of the composite glass (joining glass +
Füllstoff) zwischen 7,5 -9- 10"6 / K Filler) between 7.5 -9- 10 "6 / K
· Verträglichkeit mit Standardfüllstoffen: Cordierit, Beta Eukryptit, · Compatibility with standard fillers: Cordierite, Beta Eukryptit,
zwischen 1 -25 Gew. %  between 1 and 25% by weight
Erweichungsbeginn des Glases > 300°C (Der Erweichungsbeginn > 300°C ist notwendig, um einen ausreichenden Binderausbrand des Glases mit  Start of softening of the glass> 300 ° C (The beginning of softening> 300 ° C is necessary to ensure sufficient binder burnout of the glass with
Standardmedien zu gewährleisten.)  Standard media.)
· Keine Kristallisation der Gläser in Pulverform zwischen 300-420°C · No crystallization of the glasses in powder form between 300-420 ° C
Feuchtebeständigkeit, geringe Wasserlöslichkeit  Moisture resistance, low water solubility
Gute Anbindung des Glases auf Floatglas (sowohl auf Bad, als auch Luftseite), Verträglichkeit der Glases mit Standardlösemitteln BDG, DPM Good bonding of the glass to float glass (both on the bath side and on the air side), Compatibility of glass with standard solvents BDG, DPM
Verarbeitung unter Luft  Processing under air
Möglichkeit der Prozessierung durch schnelle Aufheizrampen und  Possibility of processing by fast heating ramps and
Abkühlrampen  cooling ramps
· bleifrei, cadmiumfrei · Unleaded, cadmium-free
Gewährleistung eines hermetischen, spannungsarmen Glas/Glasverbundes industrielle Verarbeitung mittels Dispensen, Digitaldrucktechnik, Siebdruck etc. möglich Aufgrund der niedrigen Fügetemperatur können auch thermisch vorgespannte  Ensuring a hermetic, stress-relieved glass / glass composite Industrial processing by means of dispensing, digital printing technology, screen printing etc. possible Due to the low joint temperature, thermally toughened glass can also be used
Glasscheiben gefügt werden, ohne dass sie Ihre Vorspannung verlieren. Zudem ist es durch die verhältnismäßig niedrigen Fügetemperaturen möglich, beschichtete  Glass panels are joined without losing their preload. In addition, it is possible due to the relatively low joining temperatures, coated
Floatgläser zu verarbeiten, ohne dass das Coating(low-E) der Gläser Schaden nimmt. Das erleichtert einen einfacheren Aufbau, da durch die Verwendung von dünneren Scheiben Gewicht eingespart werden kann. Andere Anwendungen im Bereich der leitfähigen Glaspasten (Solarzellenanwendungen), als Zusätze für Autoglasfarben, sind ebenfalls denkbar. To process float glass without damaging the coating (low-E) of the glasses. This facilitates a simpler structure, since by the use of thinner slices weight can be saved. Other applications in the field of conductive glass pastes (solar cell applications), as additives for automotive glass paints, are also conceivable.
Das Te02-V205-Glas besteht vorzugsweise aus The Te0 2 -V 2 0 5 glass is preferably made
Te02 40-61 Gew.-%, Te0 2 40-61% by weight,
V205 9-40 Gew.-%,V 2 0 5 9-40% by weight,
Ein bevorzugter Bereich liegt bei A preferred range is included
Te02 50-61 Gew.-%, Te0 2 50-61% by weight,
V205 20-35 Gew.-%,V 2 0 5 20-35% by weight,
Ganz besonders bevorzugt ist der Einsatz des folgenden Glases: Te02 56,00 Gew.-%,Very particularly preferred is the use of the following glass: Te0 2 56.00% by weight,
Al203 12,00 Gew.-%. Al 2 O 3 12.00 wt .-%.
Das Hochtemperaturglas besteht vorzugsweise aus Bismutglas, mit The high-temperature glass is preferably made of bismuth glass, with
Bi203 im Bereich von 75-85 Gew.-%, Bi 2 O 3 in the range of 75-85% by weight,
ZnO im Bereich von 9-15 Gew.-% und  ZnO in the range of 9-15 wt .-% and
B203 im Bereich von 5-12 Gew.-%. B 2 0 3 in the range of 5-12 wt .-%.
Die reaktiven Oxide sind vorzugsweise aus der Gruppe ausgewählt, die aus Al203, Y2O3, La203, ZnO, Bi203, Si02, Zr02, Zircon, Nb205 oder Kombinationen davon besteht. Besonders bevorzugt sind die reaktiven Oxide aus der Gruppe ausgewählt, die aus Al203, Y203, Bi203, ZnO oder Kombinationen davon besteht. The reactive oxides are preferably selected from the group consisting of Al 2 0 3, Y 2 O 3, La 2 0 3, ZnO, Bi 2 0 3, Si0 2, Zr0 2, zircon, Nb 2 0 5 or combinations thereof , The reactive oxides are particularly preferably selected from the group consisting of Al 2 O 3 , Y 2 O 3 , Bi 2 O 3 , ZnO or combinations thereof.
Ein weiterer Aspekt der Erfindung ist ein Kompositglas, das neben dem Another aspect of the invention is a composite glass, in addition to the
erfindungsgemäßen Glas ferner einen Füllstoff umfasst. glass according to the invention further comprises a filler.
Dieser Füllstoff liegt im Bereich zwischen 1 -25 Gew.-% und wird aus Cordierit oder Eukryptit ausgewählt. Bevorzugt ist ein Füllstoff bereich von 20-25 Gew.-%.  This filler is in the range of 1 to 25% by weight and is selected from cordierite or eucryptite. Preferred is a filler range of 20-25 wt .-%.
Ferner ist Gegenstand der Erfindung eine Glaspaste, die aus dem erfindungsgemäßen Glas oder aus dem erfindungsgemäßen Kompositglas mittels eines Siebdruckmediums hergestellt wird. Bevorzugt ist es, dass die Glaspaste ein Bindemittel umfasst. Hier kommt bevorzugt ein Polypropylencarbonat zum Einsatz. The invention further provides a glass paste which is produced from the glass according to the invention or from the composite glass according to the invention by means of a screen-printing medium. It is preferred that the glass paste comprises a binder. Here preferably a polypropylene carbonate is used.
Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur Herstellung eines Another object of the invention is a method for producing a
Vakuumisolierglases. Bei dem hier dargestellten Verfahren wird das erfindungsgemäße Glaslot in Form einer Paste verwendet, was allerdings nur beispielhaft dargestellt werden soll. Alternativ können auch das Glaslot selbst bzw. das Kompositmaterial zur Herstellung eines Vakuumisolierglases verwendet werden. Das Verfahren zeichnet sich durch die folgenden Schritte aus: Vacuum insulating glazing. In the method shown here, the glass solder according to the invention is used in the form of a paste, which should, however, only be illustrated by way of example. Alternatively, the glass solder itself or the composite material can also be used to produce a vacuum insulating glass. The process is characterized by the following steps:
Aufbringen der Glaspaste nach den Ansprüchen 8-9 auf ein Glassubstrat, Trocknen der Paste auf dem Glassubstrat für 10 Minuten bei  Applying the glass paste according to claims 8-9 to a glass substrate, drying the paste on the glass substrate for 10 minutes
130 °C,  130 ° C,
Erhitzen des Glassubstrates auf eine Temperatur von 300 °C für 30-60 Minuten, Hochheizen auf eine Fügetemperatur von 325-390 °C für 1 -5 Minuten,  Heating the glass substrate to a temperature of 300 ° C for 30-60 minutes, heating to a bonding temperature of 325-390 ° C for 1 -5 minutes,
Abkühlen auf Raumtemperatur,  Cooling to room temperature,
Anbringen eines zweiten Glassubstrates,  Attaching a second glass substrate,
- Hochheizen auf eine Fügetemperatur von 325-390 °C für 10-15 Minuten und Evakuieren des Glases/Glasverbunds während dem Abkühlen auf - Heating up to a bonding temperature of 325-390 ° C for 10-15 minutes and evacuation of the glass / glass composite during cooling on
Raumtemperatur.  Room temperature.
Ein weiterer Gegenstand der Erfindung ist das Vakuumisolierglas, welches durch das oben beschriebene Verfahren hergestellt wurde. Another object of the invention is the vacuum insulating glass, which was prepared by the method described above.
Das erfindungsgemäße Glaslot, das erfindungsgemäße Kompositglas und die erfindungsgemäße Glaspaste finden als Fügematerial für Glasscheiben zur Herstellung von Vakuumisoliergläsern Verwendung. The glass solder according to the invention, the composite glass according to the invention and the glass paste according to the invention are used as joining material for glass panes for the production of vacuum insulating glasses.
Daneben kommt eine Verwendung als Fügematerial für Solarzellenanwendungen und als Zusätze für Autoglasfarben in Betracht. In addition, a use as joining material for solar cell applications and as additives for automotive glass paints into consideration.
Für die Herstellung der Fügegläser können folgende Rohstoffe verwendet werden: · Telluroxidpulver 75-80% d50= 3-10 μηι The following raw materials can be used for the production of the joining glasses: tellurium oxide powder 75-80% d50 = 3-10 μηι
Vanadiumpentoxid V20595-99% Vanadium pentoxide V 2 0 5 95-99%
Calciniertes Aluminiumoxid  Calcined alumina
Die Rohstoffe werden in einem Planetenmischer, Schaufelmischer etc. gut durchmischt und in einem keramischen Tiegel, Feuerfestmaterial unter Luft bei 650- 750°C im Elektroofen geschmolzen. Die niedrigen Schmelztemperaturen sind notwendig um eine Verdampfung des TeC>2 zu verhindern. Oxidierende Schmelzführung ist notwendig, jedoch kein 02-Bubbling. The raw materials are thoroughly mixed in a planetary mixer, paddle mixer, etc. and melted in a ceramic crucible, refractory under air at 650-750 ° C in an electric furnace. The low melting temperatures are necessary to prevent evaporation of the TeC> 2. Oxidizing melt routing is necessary, but no 02 bubbling.
Das Abschrecken kann in Wasser oder wahlweise auf wassergekühlten Walzen erfolgen. Das Glas hat eine rötliche, braun schwarze Farbe. Eine Abschreckung des Glases ist aufgrund der niedrigen Viskosität des Glases auf einer Walze nicht trivial. Hier empfiehlt sich ein Guss bei Temperaturen von ca. 650°C. Um das anschließende Wiederverschmelzen des Glases untereinander zu verhindern, empfiehlt sich die Verwendung von doppelt rotierenden Walzen. Anschließend wird die abgeschreckte Fritte in Kugelmühlen, Strahlmühlen etc. auf Korngrößen d90^60 μηη aufgemahlen. Die Einstellung des WAK erfolgt wahlweise bereits beim Mahlen durch Zugabe eines keramischen Füllstoffes oder in einem abschließenden Mischschritt. Für die Herstellung des Glases wird das Glas mit einem Siebdruckmedium 801022 oder 801026 über einen Dreiwalzenstuhl zu einer Paste verarbeitet. Quenching may be in water or alternatively on water-cooled rolls. The glass has a reddish, brown black color. Quenching the glass is not trivial due to the low viscosity of the glass on a roll. Here a casting is recommended at temperatures of approx. 650 ° C. In order to prevent the subsequent re-fusion of the glass with each other, the use of double-rotating rollers is recommended. Subsequently, the quenched frit in ball mills, jet mills, etc. is ground to particle sizes d90 ^ 60 μηη. The CTE can be adjusted either during grinding by adding a ceramic filler or in a final mixing step. For the production of the glass, the glass is processed with a screen printing medium 801022 or 801026 via a three-roll mill to form a paste.
Bevorzugt kann das Glas mit einem Bindemittel aus Polypropylencarbonat (z.B. QPac 40 Binder Firma: Empower materials, USA) verarbeitet werden. Dieses Bindemittel bringt den Vorteil mit, dass es sich bereits bei Temperaturen zwischen 250-300°C zersetzt und damit ist gewährleistet, dass keine Kohlenstoffreste im Fügeglas Preferably, the glass may be processed with a polypropylene carbonate binder (e.g., QPac 40 binder company: Empower materials, USA). This binder has the advantage that it decomposes at temperatures between 250-300 ° C and thus ensures that no carbon residues in the joining glass
eingeschlossen bleiben. stay trapped.
Die Gläser werden dann mittels eines Dispensers auf das Glassubstrat aufgetragen: h= 0,3-0,5mm, b= 4- 6mm und die Paste wird mit dem Floatglas für 10 Minuten bei 130°C getrocknet. Idealerweise wird die mit Glaslot-beschichtete Floatglasscheibe in einem Ofen mit elektrisch beheizten Infrarotelementen auf eine Temperatur von 300°C gebracht und dort für 30-60 Minuten gehalten, anschließend auf die Fügetemperatur von 325-390°C hochgeheizt, 1 -5 Minuten gehalten und wieder auf Raumtemperatur abgekühlt. In einem zweiten Prozessschritt kann die zweite Floatglasscheibe auf die vorbeschichtete Floatglasscheibe platziert und mittels Klemmen mechanisch fixiert werden. Abstandshalter zwischen den Scheiben sorgen für eine gleichmäßige Lothöhe. In dem folgenden Brennzyklus wird der Verbund direkt auf die Fügetemperatur von 325- 390°C gebracht und dort für 10-15 Minuten gehalten. Abschließend wird der Verbund wieder auf Raumtemperatur abgekühlt. Mit diesem Verfahren ist gewährleistet, dass der Verbund weitgehend porenfrei ist, da der Binder vorher bei 300°C ausgebrannt wurde. Einzelne Verfahrensschritte werden bei reduziertem Atmosphärendruck wie leichtes Vakuum (ca. 100-600 mbar), mittleres Vakuum (ca. 0,1 -100 mbar) und Hochvakuum (<0,01 mbar) durchgeführt, um die Porenbildung zu steuern. The glasses are then applied to the glass substrate by means of a dispenser: h = 0.3-0.5mm, b = 4-6mm and the paste is dried with the float glass for 10 minutes at 130 ° C. Ideally, the glass solder-coated float glass in an oven with electrically heated infrared elements to a temperature of 300 ° C and held there for 30-60 minutes, then heated to the bonding temperature of 325-390 ° C, held for 1-5 minutes and cooled again to room temperature. In a second process step, the second float glass pane can be placed on the pre-coated float glass pane and mechanically fixed by means of clamping. Spacers between the discs ensure a uniform height of solder. In the following firing cycle, the composite is brought directly to the bonding temperature of 325- 390 ° C and held there for 10-15 minutes. Finally, the composite is cooled again to room temperature. This process ensures that the composite is largely free of pores, since the binder was previously burned out at 300 ° C. Individual process steps are carried out at reduced atmospheric pressure such as light vacuum (about 100-600 mbar), medium vacuum (about 0.1-100 mbar) and high vacuum (<0.01 mbar) to control pore formation.
Die Erfindung wird nachfolgend anhand von Beispielen beschrieben, die die Erfindung nicht einschränken. The invention will now be described by way of examples, which do not limit the invention.
Ausführungsbeispiele embodiments
Es wurden Hochtemperaturgläsern, ausgewählt aus der Gruppe die aus Bleiglas, Bismutglas, Zinkglas, Bariumglas, Calciumglas, Alkalisilikatglas im Bereich von 0,5-20 Gew.-% besteht, zu den Fügeglasmischungen aus der PCT/EP2015/072207 gegeben. Hier zeigte sich ein vorteilhafter Effekt bei Fügebedingungen im Vakuum High-temperature glasses selected from the group consisting of lead glass, bismuth glass, zinc glass, barium glass, calcium glass, alkali silicate glass in the range of 0.5-20% by weight were added to the joining glass mixtures from PCT / EP2015 / 072207. Here was an advantageous effect at joining conditions in a vacuum
Weiterhin wurden reaktive Oxide, ausgewählt aus der Gruppe die aus AI2O3, Y2O3, La2O3, ZnO, Bi2O3, SiO2, ZrO2, Zircon, Nb2O5, V2O5, TeO2, CeO2, SnO, SnO2, FeO,Furthermore, reactive oxides selected from the group consisting of Al 2 O 3 , Y 2 O 3 , La 2 O 3 , ZnO, Bi 2 O 3 , SiO 2 , ZrO 2 , zirconium, Nb 2 O 5 , V 2 O 5 , TeO 2 , CeO 2 , SnO, SnO 2 , FeO,
MnO, Cr2O3, CoO, Oxidpigmente, oder einer Kombination davon, im Bereich von 0,5-20 Gew.-% besteht, zu den Fügeglasmischungen aus der PCT/EP2015/072207 gegeben. Die Teilchengröße der reaktiven Oxide beträgt dabei 0,1 -40 μηη, vorzugsweise 0,1 bis 20 μπι. MnO, Cr 2 O 3, CoO, oxide pigments, or a combination thereof, in the range of 0.5-20 wt .-%, added to the joining glass mixtures from PCT / EP2015 / 072207. The particle size of the reactive oxides is 0.1 to 40 μηη, preferably 0.1 to 20 μπι.
Testbedingungen: Pellettest und Fließtest sowohl bei Test conditions: pellet test and flow test both at
Atmosphärendruckbrennbedingungen als auch bei Vakuumbrennbedingungen bei 400, 100, 10, 0,1 und 0,01 mbar.  Atmospheric pressure firing conditions as well as vacuum firing conditions at 400, 100, 10, 0.1 and 0.01 mbar.
Erfolgskriterien: Benetzung und Bindung an das Glassubstrat kein Schäumen bei den Pellet-Tests, wie auch bei den Querschnitten  Success criteria: Wetting and bonding to the glass substrate no foaming in the pellet tests, as well as in the cross sections
Die Ergebnisse sind vielversprechend, es findet eine gute Bindung an das Floatglas statt. Fluss bei Temperaturen < 450°C, stärker bevorzugt < 420°C, kein Schäumen beim Vakuumbrennen. The results are promising, there is a good bond to the float glass instead. Flow at temperatures <450 ° C, more preferably <420 ° C, no foaming at Vacuum baking.
Bevorzugte reaktive Oxide: Y2O3, ZnO, Bi2O3, AI2O3 Preferred reactive oxides: Y 2 O 3 , ZnO, Bi 2 O 3 , Al 2 O 3
Es können auch Mischungen der reaktiven Oxide verwendet werden.  It is also possible to use mixtures of the reactive oxides.
Auch ist denkbar, nach dem Anlegen von Vakuum die Vakuumvorrichtung mit It is also conceivable, after the application of vacuum, the vacuum device with
Schutzgas (N2 oder Argon) zu befüllen, um bestimmte Komponenten während dem Fügeprozess zu schützen. Im nachfolgenden werden zwei Beispiele konkret beschrieben. Inert gas (N 2 or argon) to protect certain components during the joining process. In the following two examples will be described concretely.
Beispiel 1 : Zusatz von verschiedenen Mengen eines Bismut-haltigen Glases zu einem Tellur-Vanadiumglas Zu TDF9533a wurden 5% Gew.-% bzw. 10 Gew.-% EG9824 gegeben. (TDF9533a, Zusammensetzung TeO2 56,00 Gew.-%, V2O5 32,00 Gew.-% und AI2O3 12,00 Gew.-%, EG9824A7: Bi2O3-ZnO-B2O3-Glas). Aus Tabelle 1 erkennt man deutlich die Erhöhung des Erweichungspunktes und der jeweiligen Temperaturen bei steigender Konzentration von EG9824. Example 1: Addition of various amounts of a bismuth-containing glass to a tellurium vanadium glass To TDF9533a were added 5% by weight and 10% by weight of EG9824, respectively. (TDF9533a, composition TeO 2 56.00 wt.%, V 2 O 5 32.00 wt.% And Al 2 O 3 12.00 wt.%, EG9824A7: Bi 2 O 3 -ZnO-B 2 O 3 glass). Table 1 clearly shows the increase in the softening point and the respective temperatures with increasing concentration of EG9824.
Tabelle 1 : Table 1 :
Erhitzungsmikroskopie TDF9533a TDF9533a TDF9533a  Heating microscopy TDF9533a TDF9533a TDF9533a
Zusatz Bi-Glas  Addition Bi-glass
Wt.-% 0 5 10 Wt .-% 0 5 10
Vol.-% 0 2,9 6Vol .-% 0 2.9 6
Erweichungspunkt (°C) 352 352 372Softening point (° C) 352 352 372
Sphärischtemperatur (°C) 377 386 413Spherical temperature (° C) 377 386 413
Halbkugeltemperatur (°C) 435 452 505Hemisphere temperature (° C) 435 452 505
Fließtemperatur (°C) 920 985 992 Beispiel 2: Zusatz von verschiedenen Mengen AI2O3 zu einem Tellur-Vanadiumglas Flow temperature (° C) 920 985 992 Example 2: Addition of different amounts of Al 2 O 3 to a tellurium vanadium glass
Tabelle 2: Table 2:
Beispiel 3 Zusatz von verschiedenen Mengen Si02 zu einem Tellur-Vanadiumglas Example 3 Addition of different amounts of SiO 2 to a tellurium vanadium glass
Tabelle 3: Table 3:
Wenn in der Tabelle keine Angaben sind, wird die Temperatur nicht erreicht. If there is no information in the table, the temperature will not be reached.
Die Änderungen des Erweichungspunktes, Spärischtemperatur bei Vol.-% 0 liegen an der Verwendung unterschiedlicher Partikelgrößen des Cordierit-Füllstoffes. Als geeignet hat sich eine Partikelgröße von Cordierit von d50 ca. 20 μηη erwiesen.  The changes in the softening point, the storage temperature at Vol .-% 0 are due to the use of different particle sizes of the cordierite filler. A particle size of cordierite of d50 has proven to be suitable for approximately 20 μm.
Figur 1 zeigt die Abhängigkeit der Sphärischtemperatur von der Volumenkonzentration des Additivs. FIG. 1 shows the dependence of the sphere temperature on the volume concentration of the additive.

Claims

Patentansprüche  claims
Glas, insbesondere Fügeglas, umfassend die nachfolgenden Komponenten in Gew.-%: Glass, in particular joint glass, comprising the following components in% by weight:
Te02-V205-Glas im Bereich von 60-100 Gew.-%, Te0 2 -V 2 0 5 glass in the range of 60-100 wt .-%,
Hochtemperaturgläser, ausgewählt aus der Gruppe, die aus Bleiglas, Bismutglas, Zinkglas, Bariumglas, Calciumglas, Alkalisilikatglas im Bereich von 0-20 Gew.-% besteht und  High temperature glasses selected from the group consisting of lead glass, bismuth glass, zinc glass, barium glass, calcium glass, alkali silicate glass in the range of 0-20% by weight, and
reaktive Oxide, ausgewählt aus der Gruppe, die aus Al203, Y203, La203, ZnO, Bi203, Si02, Zr02, Zircon, Nb205, V205, Te02, Ce02, SnO, Sn02, FeO, MnO, Cr203, CoO, Oxidpigmenten, oder einer Kombination davon, im Bereich von 0-20 Gew.-% besteht. reactive oxides selected from the group consisting of Al 2 0 3, Y 2 0 3, La 2 0 3, ZnO, Bi 2 0 3, Si0 2, Zr0 2, zircon, Nb 2 0 5, V 2 0 5, TeO 2 , CeO 2 , SnO, SnO 2 , FeO, MnO, Cr 2 O 3 , CoO, oxide pigments, or a combination thereof, in the range of 0-20% by weight.
Glas, insbesondere Fügeglas, umfassend die nachfolgenden Komponenten in Gew.-%: Glass, in particular joint glass, comprising the following components in% by weight:
Te02-V205-Glas im Bereich von 60-100 Gew.-%, Te0 2 -V 2 0 5 glass in the range of 60-100 wt .-%,
Hochtemperaturgläser, ausgewählt aus der Gruppe, die aus Bleiglas, Bismutglas, Zinkglas, Bariumglas, Calciumglas, Alkalisilikatglas im Bereich von 0,5-20 Gew.-% besteht und  High temperature glasses selected from the group consisting of lead glass, bismuth glass, zinc glass, barium glass, calcium glass, alkali silicate glass in the range of 0.5-20% by weight, and
reaktive Oxide, ausgewählt aus der Gruppe, die aus Al203, Y203, La203, ZnO, Bi203, Si02, Zr02, Zircon, Nb205, V205, Te02, Ce02, SnO, Sn02, FeO, MnO, Cr203, CoO, Oxidpigmenten, oder einer Kombination davon, im Bereich von 0,5-20 Gew.-% besteht. reactive oxides selected from the group consisting of Al 2 0 3, Y 2 0 3, La 2 0 3, ZnO, Bi 2 0 3, Si0 2, Zr0 2, zircon, Nb 2 0 5, V 2 0 5, TeO 2 , CeO 2 , SnO, SnO 2 , FeO, MnO, Cr 2 O 3 , CoO, oxide pigments, or a combination thereof, in the range of 0.5-20% by weight.
Glas nach den Ansprüchen 1 -2 wobei das Te02-V205-Glas aus Glass according to claims 1-2, wherein the Te0 2 -V 2 0 5 glass
Te02 40-61 Gew.-%, Te0 2 40-61% by weight,
V205 9-40 Gew.-%, V 2 0 5 9-40% by weight,
Al203 5-20 Gew.-% Al 2 O 3 5-20% by weight
besteht. Glas nach Anspruch 3, wobei das TeO2-V2O5-Glas aus consists. A glass according to claim 3 wherein the TeO 2 V 2 O 5 glass is
TeO2 50-61 Gew.-%, TeO 2 50-61% by weight,
V2O5 20-35 Gew.-%,V 2 O 5 20-35% by weight,
besteht.  consists.
Glas nach einem der Ansprüche 1 -4, wobei das Hochtemperaturglas ausGlass according to any one of claims 1-4, wherein the high temperature glass is made
Bismutglas besteht, mit Bismuth glass persists, with
B12O3 im Bereich von 75-85 Gew.-%,  B12O3 in the range of 75-85% by weight,
ZnO im Bereich von 8-15 Gew.-% und  ZnO in the range of 8-15 wt .-% and
B2O3 im Bereich von 5-12 Gew.-%. B 2 O 3 in the range of 5-12 wt .-%.
Glas nach einem der Ansprüche 1 -5, wobei die reaktiven Oxide, aus der Gruppe ausgewählt sind, die aus AI2O3, Y2O3, La2O3, ZnO, Bi2O3, SiO2, ZrO2, Zircon, Nb2O5 oder Kombinationen davon besteht. A glass according to any one of claims 1-5, wherein the reactive oxides are selected from the group consisting of Al 2 O 3 , Y 2 O 3 , La 2 O 3 , ZnO, Bi 2 O 3 , SiO 2 , ZrO 2 , Zircon, Nb 2 O 5 or combinations thereof.
Glas nach Anspruch 6, wobei die reaktiven Oxide, aus der Gruppe ausgewählt sind, die aus AI2O3, Y2O3, Bi2O3, ZnO oder Kombinationen davon besteht. A glass according to claim 6, wherein the reactive oxides are selected from the group consisting of Al 2 O 3, Y 2 O 3, Bi 2 O 3, ZnO, or combinations thereof.
Kompositglas, dadurch gekennzeichnet, dass es das Glas nach einem der Ansprüche 1-7 und ferner einen Füllstoff umfasst. Composite glass, characterized in that it comprises the glass according to any one of claims 1-7 and further a filler.
Kompositglas nach Anspruch 8, dadurch gekennzeichnet, dass der Füllstoff im Bereich zwischen 1-25 Gew.-% liegt. Composite glass according to claim 8, characterized in that the filler is in the range between 1-25 wt .-%.
Kompositglas nach den Ansprüchen 8-9, dadurch gekennzeichnet, dass der Füllstoff aus Cordierit oder Eukryptit ausgewählt wird. Composite glass according to claims 8-9, characterized in that the filler is selected from cordierite or eukryptite.
Glaspaste, hergestellt aus dem Glas nach den Ansprüchen 1 -7 oder aus dem Kompositglas nach den Ansprüchen 8-10 mittels eines Siebdruckmediums. Glass paste produced from the glass according to claims 1-7 or from the composite glass according to claims 8-10 by means of a screen-printing medium.
12. Glaspaste nach Anspruch 1 1 , umfassend ferner ein Bindemittel. Verfahren zur Herstellung eines Vakuumisolierglases, gekennzeichnet durch die folgenden Schritte: 12. Glass paste according to claim 1 1, further comprising a binder. Method for producing a vacuum insulating glass, characterized by the following steps:
Aufbringen der Glaspaste nach den Ansprüchen 11 -12 auf ein Applying the glass paste according to claims 11-12 on a
Glassubstrat, Glass substrate,
Trocknen der Paste auf dem Glassubstrat für 10 Minuten bei 130 °C,  Drying the paste on the glass substrate for 10 minutes at 130 ° C,
Erhitzen des Glassubstrates auf eine Temperatur von 300 °C für 30-60 Minuten,  Heating the glass substrate to a temperature of 300 ° C for 30-60 minutes,
Hochheizen auf eine Fügetemperatur von 325-390 °C für 1 -5 Minuten, Abkühlen auf Raumtemperatur,  Heating to a bonding temperature of 325-390 ° C for 1-5 minutes, cooling to room temperature,
Anbringen eines zweiten Glassubstrates,  Attaching a second glass substrate,
Hochheizen auf eine Fügetemperatur von 325-390 °C für 10-15 Minuten und  Heating up to a bonding temperature of 325-390 ° C for 10-15 minutes and
Evakuieren des Glases/Glasverbunds während dem Abkühlen auf  Evacuate the glass / glass composite during cooling
Raumtemperatur.  Room temperature.
Verfahren nach Anspruch 13, wobei einzelne Verfahrensschritte bei reduziertem Atmosphärendruck wie leichtes Vakuum (ca. 100-600 mbar), mittleres Vakuum (ca. 0,1 -100 mbar) und Hochvakuum (<0,01 mbar) durchgeführt werden. The method of claim 13, wherein individual process steps at reduced atmospheric pressure such as light vacuum (about 100-600 mbar), medium vacuum (about 0.1 to 100 mbar) and high vacuum (<0.01 mbar) are performed.
15. Vakuumisolierglas, hergestellt nach dem Verfahren nach den Ansprüchen 13-14. 15. vacuum insulating glass, prepared by the method according to claims 13-14.
16. Verwendung des Glases nach einem der Ansprüche 1-7 oder des 16. Use of the glass according to any one of claims 1-7 or of
Kompositglases nach den Ansprüchen 8-10 oder der Glaspaste nach den Ansprüchen 1 1 -12 als Fügematerial für Glasscheiben zur Herstellung von Composite glass according to claims 8-10 or the glass paste according to claims 1 1 -12 as joining material for glass panes for the production of
Vakuumisoliergläsern. Vakuumisoliergläsern.
17. Verwendung des Glases nach einem der Ansprüche 1-7 oder des 17. Use of the glass according to any one of claims 1-7 or of
Kompositglases nach den Ansprüchen 8-10 oder der Glaspaste nach den Ansprüchen 1 1 -12 als Fügematerial für Solarzellenanwendungen und als Zusätze für Autoglasfarben.  Composite glass according to claims 8-10 or the glass paste according to claims 1 1 -12 as joining material for solar cell applications and as additives for automotive glass paints.
EP17717379.6A 2016-05-23 2017-04-11 Low-temperature tellurite glass mixtures for vacuum compaction at temperatures up to 450 °c Active EP3414209B1 (en)

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